Adducts



ADDUCTS Joachim Dazzi, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application February 25, 1954 Serial No. 412,631

13 Claims. (Cl. 260-4045) This invention relates to new condensation products formed by reaction of :,[3-1111Sfitll13t6d, dicarboxylic acid derivatives with certain fatty oils. More particularly, it relates to new condensation products formed by reaction of certain fumarates with olefinic, unconjugated, non-hydroxylated fatty oils having from to 24 carbon atoms in each fatty acid portion thereof, and to methods of producing the same.

The reaction of certain a,B-t1nsaturated acid derivatives with higher olefinic fatty oils is well known in the art. Numerous instances in the literature disclose the formation of adducts from maleic anhydride and the higher olefinic fatty oils such as olive oil, soya bean oil, etc. Prior art teachings concerning reactions involving a,B-unsaturated dicarboxylic acid derivatives and olefinic fatty acids indicate that (1) Maleic anhydride and compounds which give maleic anhydride under the reaction conditions are generally equivalents in the reaction, but that r (2) Maleates give less viscous products than does maleic anhydride when reacted with the unsaturated oils, and that (3) Only as many maleic acid residues may be introduced into the fatty oil as there areolefinic double bonds in the fatty acid portions thereof.

The above beliefs concerning the preparation of 11,5- mono-olefinic dicarboxylic adducts with the unsaturated fatty oils has materially affected the potential usefulness of such adducts; for, while the adducts were granted to have an intersecting structure with respect to potential chemical reactivity, in practice it has been difficult to prepare products of uniformly good physical attributes. Stemming from the knowledge that the maleates were not so reactive as maleic anhydride, the latter has been preferred almost exclusively as the dicarboxy component in reactions of this type. However, adducts from maleic anhydride have been generally of very poor color. For example, the color of adducts of maleic anhydride and a fatty oil such as soya bean oil generally varies from dark brown to black, even though the starting materials are light yellow.

Now, I have found that, contrary to prior art teachings, esters of atfl-mono-olefinic dicarboxylic acids are neither general equivalents of maleic anhydride nor generally less reactive than maleic anhydride in reactions with the unsaturated fatty oils, and that when alkyl esters of fumaric acid are used as the dicarboxy components, there are obtainable adducts having a number of succinic acid residues which is greater than the total number of olefinic double bonds of the fatty acid portions of the glyceride oils. The present invention thus provides an adduct of an olefinic non-conjugated, non-hydroxylated fatty oil having from 10 to 24 carbon atoms in each fatty acid portion thereof and an alkyl fumarate having from 1 to 8 carbon atoms in the alkyl radical, said adduct being characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds Stas atent O present in said oil. Such adducts may be represented by the following formula CHr-CHCH in which Y and R are alkyl radicals of from 1 to 8 carbon atoms, T is a non-conjugated, aliphatic olefinic hydrocarbon radical of from 9 to 23 carbon atoms and in which the sum of x, y and z is greater than the sum of the olefinic double bonds present in all of said hydrocarbon residues.

Esters of fumaric acid which may be reacted with the non-conjugated, non-hydroxylated fatty oils to yield the presently useful adducts are simple or mixed dialkyl fumarates in which each alkyl radical has from 1 to 8 carbon atoms, e. g., methyl, ethyl, propyl, isopropyl, or n-butyl fumarate, ethyl methyl fumarate, isobutyl propyl fumarate, amyl fumarate, hexyl fumarate, 2-ethyl-hexyl fumarate, n-octyl fumarate, amyl heptyl fumarate, 2- ethyl-hexyl isopropyl fumarate, etc. As examples of useful fatty oils for the present purpose may be mentioned soy bean oil, safflower oil, olive oil, linseed oil, corn oil, peanut oil, perilla oil, salmon oil, menhaden oil, cotton seed oil, etc.

While isomeric mixtures are possible, and the position to which the fumarate residue is attached to the fatty acid portion of the triglyceride oils is not known, the re action of, e. g., four moles of a dialkyl fumarate with one mole of an unsaturated, non-conjugated fatty oil such as olive oil may be illustrated by noting the probable reaction scheme with oleic acid triglyceride, the major component of olive oil:

CH3(OH2) OH:OH(OH2) COOCH CHCOOY 11200011 J1 OHa(CHa)CHCH:OH(OH2)EEOOOC z onoooY OHaCOOR in which Y and R are as defined above, and x is a whole number between 5 and 8.

It is to be noted that the above-depicted 1:4 olive oilfumarate adduct still contains the olefinic groups of the original fatty oils. Adducts in which two carboalkoxy radicals are attached to each of the fatty acid portions are obtained by simply heating the 1:4 adduct with two additional equivalents of fumarate. Adducts in which three carboalkoxy radicalsare attached to one or more of the fatty acid portions are formed when the 1:6 adducts are heated with more fumarate, the reaction in this case proceeding probably with addition of a carboalkoxy group at the unsubstituted carbon which is adjacent to the carbon attached to the olefinic double bond. Additional fumarate and longer heating results in the formation of adducts in which each of the carbon atoms which are adjacent to those having an olefinic double bond has two carboalkoxy radicals attached thereto. Depending upon the quantity of fumarate present in the reaction mixture,

respective intermediate portions of each mono-olefinic chain of the triglyceride, the olefinic double-bond in each case remaining unsaturated. Generally, reaction of the glycerides with the fumarate results in a mixture of adducts in which up to 4 moles of fumarate per olefinic double bond of the oil have combined with the oil.

Reaction of the fatty oils with the fumarate to form the present adducts takes place readily by heating the oil with the ester in the presence or absence of an inert diluent or solvent at ordinary or superatmospheric pressures. Catalysts may or may not be employed. When operating at atmospheric pressure, temperatures of from, say, 150- C. to 300 C. and preferably of from 200 C. to 280 C. are used. When Working with readily polymerizable fumarates, an inhibitor of polymerization may be incorporated into the reaction mixture. The number of carboalkoxy groups introduced into the oil depends upon the quantity and nature of the individual ester used, and upon the reaction conditions employed. Generally, operation Within the higher temperature ranges, i. e., at temperatures of above, say, 180 C. and below the decomposition point of any of the reactants leads to introduction of more carboalkoxy groups than does operation at the lower temperatures. Usually, the lower alkyl fumarates are more reactive than the higher alkyl fumarates. In view of the effect of the reaction conditions and nature of the fumarates upon the extent of carboalkoxylation, it is recommended that for each initial run there be experimentally determined the operating conditions which should be observed for obtaining the desired degree of carboalkoxylation.

Since the presently useful esters are generally miscible with most of the unsaturated oils under the reaction conditions used, no extraneous solvent or diluent usually need be employed. However, in order to facilitate handling of some of the oils, it may be advantageous to work in an inert, extraneous diluent or solvent, e. g., a liquid hydrocarbon or a liquid derivative thereof such as benzene, xylene, or a high-boiling aliphatic hydrocarbon such as kerosene, halogenated aliphatic hydrocarbons, etc. When operating at atmospheric pressure such diluent is generally removed before reaction of the oil with the fumarate occurs, due to the high temperature used. For successful reaction, the diluent may or may not be present.

The reaction time may vary from, say, a few minutes to 24 hours, a reaction time of, say, from 2 to 8 hours being recommended when it is desired to obtain a preponderant yield of products having a high carboalkoxy content. The product is generally a viscous liquid which comprises a mixture of adducts of varying carboalkoxy content and unreacted initialreagents. Any unreacted material may be readily recovered, e. g., by distillation, and the residue of mixed adducts may be used as such for a variety of industrial purposes.

When alkyl fumarates, instead of maleic anhydride or the corresponding maleates, are reacted with the fatty oils, the reaction proceeds muchmore smoothly than it does with maleic anhydride and much more rapidly than it does with the maleates. The physical and chemical characteristics of the fumarate-fatty oil adducts differ remarkably from those of the maleic anhydride adducts. Whereas the latter are generally opaque and of a dark color, the present fatty oil-fumarate adducts are clear and transparent and of light color. The high carboxylate content of the present adducts recommends them for use in a variety of industrial and agricultural applications, for example as thickening agents in the preparation of emollients and greases, as blending agents in the preparation of new and improved resinous compositions, as intermediates for the preparation of surfactants, etc. As disclosed in my copending application Serial No. 333,331, filed January 26, 1953, and now issuedas'U. SQPatent No. 2,757,151, dated July 31, 1956, of which the present application is a continuation-in-part, some of the present adducts are particularly valuable as polyvinyl chloride plasticizers. Also, as disclosed in the copending application of Ival Salyer, James Herbig and Joachim Dazzi, filed March 17, 1954, Serial No. 416,958, now-U. S. Patent No. 2,824,846, when mixtures of the present adducts and monomeric styrene are subjected to polymerizing compositions, there are obtained polymeric products having strength characteristics superior to those possessed by styrene homopolymers prepared in the absence of said adducts.

The present invention is further illustrated, but not limited, by the following examples:

Example 1 To a flask equipped with reflux condenser and mechanical stirrer there were charged g. (0.15 mole) of soy bean oil and 151 g. (1.05 mole) of methyl fumarate. The mixture was refiuxed in a nitrogen atmosphere for 10 hours at 200212 C. Distillation of the resulting reaction product at a pressure of l2 mm. of mercury and also in a nitrogen atmosphere to remove unreacted fumarate gave as residue 242 g. of an adduct in which 1 mole of soy bean oil had combined with an average of 5.0 moles of methyl fumarate.

Example 2 A mixture consisting of 0.15 mole (135 g.) of soy bean oil and 1.05 moles of ethyl fumarate was heated in a nitrogen atmosphere for 10 hours at 220-245 C. (mostly 220-235 C.). Distillation of the resulting reaction mixture at a pressure of 1-2 mm. of mercury and also in a nitrogen atmosphere, gave 42 g. of unreacted ethyl fumarate. The residue (285 g.) was the yellow highly viscous ethyl fumarate--soy bean oil adduct. Based on reacted fumarate, one mole of the soy bean oil had combined with an average of 5.8 moles of the ethyl fumarate for formation of the adduct.

Example 3 A mixture consisting of 135 g. (0.15 mole) of safflower oil and 180.5 g. (1.05 mole) of ethyl fumarate was heated in the nitrogen atmosphere for about 4 hours at 230-267 C. Unreacted ethyl fumarate (40.2 g.) was then removed from the resulting reaction mixture by heating in vacuo (12 mm. Hg pressure) at an oil bath temperature of 210230 C. There was obtained as residue 275 g. of viscous, light yellow adduct n 1.4752, in which one mole of safilower oil had combined with an average of 5.04 moles of ethyl fumarate.

Example 4 A mixture consisting of 135 g. (0.15 mole) of soy bean oil and 310 g. (1.8 moles) of ethyl fumarate was heated in a nitrogen atmosphere for 10 hours at a temperature of 204 to 228 C. Distillation of the resulting reaction product to remove material boiling below 200 C./12 mm., gave 421 g. of a viscous adduct a 1.4732, in which one mole of the oil is combined with an average of 10.6 moles of the ethyl fumarate.

Example 5 A mixture consisting of 90.0 g. (0.1 mole) of soy bean oil and g. (0.7 mole) of n-butyl fumarate was heated in a nitrogen atmosphere to 250 C. within one hour and then maintained at a temperature of 250-260 C. for 5 hours. During the 5-hour period, the refractive index of the reaction mixture rose from 1.4600 to 1.4716. Distillation of the resulting reaction mixture in a nitrogen atmosphere to remove material boiling below 231 C./ 2 mm. gave as residue 236 g. of an adduct, n 1.4720, in which 1 molecular equivalent of the soy bean oil had combined with an average of 6.4 molecular equivalents of the n-butyl fumarate.

Example 6 This example shows that even after only one hour of refluxing, the reaction of soy bean oil and an alkyl fumarate leads to the production of adducts in which the number of moles of combined fumarate is greater than the number of olefinic double bonds present in the oil.

A mixture consisting of 90.0 g. (0.1 mole) of soy bean oil and 160 g. (0.7 mole) of n-butyl fumarate in a nitrogen atmosphere was brought to a temperature of 260 C. Within about 45 minutes, and then held at a temperature of 260 C. to 275 C. for one hour. Distillation of the resulting reaction mixture to remove material boiling below 231 C./2 mm. gave as residue 202 g. of the adduct, 21 1.4730, in which one mole of the soy bean oil had combined with an average of 4.96 moles of the n-butyl fumarate.

Example 7 A mixture consisting of 90 g. of safllowcr oil and 160 g. of n-butyl fumarate in a nitrogen atmosphere was brought to a temperature of 255 C. within about 20 minutes, and then held at a temperature of 254 C. to 262 C. for 2 hours. Distillation of the resulting reaction mixture gave 34.5 g. of unreacted n-butyl fumarate. The residue was an adduct, n 1.4700 in which one mole of the safilower oil is combined with an average of 5.23 moles of the n-butyl fumarate.

Example 8 A mixture consisting of 180 g. (0.2 mole) of safflower oil and 362 g. (2.10 moles) of ethyl fumarate was rapidly brought to a temperature of 100 C. At this point the refractive index of the mixture was 11 1.4520. The mixture was then heated to 212 C. within one hour and then maintained at 212 C. to 254 C. for about 8 hours. At the end of this time the reaction mixture had 11 1.4691. Distillation of this mixture to remove material boiling up to 230 C./1-2 mm. gave as residue 433 g. of the viscous, light-colored adduct, 11 1.4760, in which one mole of the safflower oil is combined with an average of 7.33 moles of the ethyl fumarate.

Example 9 This example shows testing of the adducts of some of the previous examples as plasticizers for polyvinyl chloride.

Sixty parts of polyvinyl chloride and forty parts by weight of the methyl fumarate-soy bean oil addition product of Example 1 were mixed on a rolling mill to a homogeneous blend. During the milling there was observed substantially no fuming and discoloration. A molded sheet of the mixture was clear, transparent, and substantially colorless. Testing of the molded sheet for low temperature flexibility, according to the Clash-Berg method, gave a value of minus 3. Tests on the volatility characteristics of the plasticized composition employing the carbon absorption method of Society of the Plastics Industry gave a value of 1.10 percent which showed excellent retention of plasticizer and indicated good temperature characteristics of the composition. The plasticized material had a water-absorption value of 0.55 percent and a solids-loss value of 0.081 percent after immersion in water for 24 hours. When subjected to heat at a temperature of 325 F. for a period of 30 minutes the clarity and color of the molded sheet were substantially unchanged.

When subjected to the same evaluation procedures, polyvinyl chloride plasticized with the soy bean oil-ethyl fumarate adduct of Example 2 was found to have a low temperature flexibility value of minus 3, a volatility value or 2.4 percent, a water-absorption value of 0.55 percent and a solids-loss of 0.08 percent. The molded sheets were clear, homogeneous and substantially colorless, and when subjected to heat at 325 F. for 30 minutes the good properties thereof were substantially unchanged.

When subjected to the same plasticizer evaluation procedures, polyvinyl chloride which had been plasticized with the safllower-ethyl fumarate adduct of Example 3 was found to have a low temperature flexibility value of minus 5 C., a volatility value of 1.67 percent, a waterabsorption value of 0.48 percent and a solids-loss value of 0.028 percent. The present molded sheets were homogeneous and of good, clear color. They were substantially unaffected by heating at 325 F. for 30 minutes.

Example 10 This example illustrates resistance of the present adducts to liquid hydrocarbons.

Sixty parts by weight of polyvinyl chloride and forty parts by weight of the soy bean oil-ethyl fumarate adduct 1 :5 .8 molar ratio adduct) of Example 2 were milled together to a homogeneous blend. Molded test specimens were prepared therefrom, said specimens being circles having a diameter of two inches and a thickness of 2 mm. The test specimens were immersed in kerosene for 24 hours at a temperature of 50 C., wiped dry, and then oven-dried at 50 C. for 44 hours. The dried specimens showed a weight change of plus 2.5 percent as compared to the initial weight thereof.

This non-extractibility of the present adducts by kerosene from polyvinyl chloride resins plasticized by the same is remarkable in that commonly employed plasticizers are readily extracted when submitted to the same test. Thus, like-dimensioned molded test specimens of a milled blend consisting of 60 percent polyvinyl chloride and 40 percent dioctyl phthalate suffered a weight loss of 27.5 percent when submitted to the same test.

This invention is a continuation-in-part of my copending application Serial No. 333,331, filed January 26, 1953.

What I claim is:

1. An adduct of an olefinic non-conjugated, non-hydroxylated fatty oil having from 10 to 24 carbon atoms in each fatty acid portion thereof and an alkyl fumarate having from 1 to 8 carbon atoms in the alkyl radical, said adduct being further characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

2. An adduct of soy bean oil and an alkyl fumarate having from 1 to 8 carbon atoms, said adduct being further characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

3. An adduct of safilower oil and an alkyl fumarate having from 1 to 8 carbon atoms, said adduct being fur ther characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

4. An adduct of soy bean oil and ethyl fumarate, said adduct being further characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

5. An adduct of soy bean oil and butyl fumarate, said adduct being further characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

6. An adduct of safflower oil and ethyl fumarate, said adduct being further characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

7. An adduct of saffiower oil and butyl fumarate, said adduct being further characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

8. The process which comprises heating, at a temperature of ISO-300 C., an olefinic non-conjugated, nonhydroxylated fatty oil having from 10 to 24 carbon atoms in each fatty acid portion thereof and an alkyl fumarate having from 1 to 8 carbon atoms in the alkyl radical and recovering from the resulting reaction product an adduct of said oil with said fumarate characterized by containing a total number of fuma-rate groups which is greater than the number of olefinic double bonds present in said oil.

9. The process which comprises heating soy bean oil with an alkyl fumarate having from 1 to 8 carbon atoms in the alkyl radical, at a temperature of ISO-300 C., and recovering from the resulting reaction product an adduct of said oil with said fumarate characterized by containing a total number of fumarate groups which is greater than the number, of olefinic double bonds present in said oil.

10. The process-which comprises heating soy bean oil with ethyl fumarate at a temperature of 200-280 C. and recovering from the resulting reaction product an adduct of said oil with said fumarate characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

11. The process which comprises heating soy bean oil with butyl fumarate at a temperature of ZOO-280 C. and recovering from the resulting reaction product an adduct of said oil with said furnarate characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

12. The process which comprises heating safflower oil with ethyl fumarate at a temperature of ZOO-280 C. and recovering from the resulting reaction product an adduct of said oil with said fumarate characterized by containing a total number of fumarate groups which is greater than thenumber of olefinic double bonds present in said oil. r

13. The process which comprises heating safliower oil with butyl fumarate at a temperature of ZOO-280 C. and recovering from the resulting reaction product an adduct of said oil with said fumarate characterized by containing a total number of fumarate groups which is greater than the number of olefinic double bonds present in said oil.

References Cited in the file of this patent UNITED STATES PATENTS 2,630,441 Dazzi Mar. 3, 1953 2,678,934 Grummitt May 18, 1954 2,687,421 Butler Aug. 24, 1954 

1. AN ADDUCT OF AN OLEFINIC NON-CONJUGATED, NON-HYDROXYLATED FATTY OIL HAVING FROM 10 TO 24 CARBON ATOMS IN EACH FATTY ACID PORTION THEREOF AND AN ALKYL FUMARATE HAVING FROM 1 TO 8 CARBON ATOMS IN THE ALKYL RADICAL, SAID ADDUCT BEING FURTHER CHARACTERIZED BY CONTAINING A TOTAL NUMBER OF FUMARATE GROUPS WHICH IS GREATER THAN THE NUMBER OF OLEFINIC DOUBLE BONDS PRESENT IN SAID OIL. 